Water-soluble phenolic



Patented June 23, 1936 PATENT OFFICE warm-sonnets rmmomc nsarvanvss HermanA. manners-handout stein. La'nsdowne, Pa; assignors to Rohm" & Haas Company, Phiiad elnhis, Pa.

No Drawing. Application February 18, 1935,

' Serial No. 6,386

15 The condensation of the alcohol-with the salt of the complex phenolic amine base takespiace readily upon heating the mixture atfrom about 80 to 200 C. under ordinary atmospheric pressure. The condensation is advantageously carried 20 out in the presence of an inert, volatile, organic liquid which boils within the above temperature range and which can subsequently be removed 'by distillation. 7 Suitable liquids for thepur se are toluene, xylene, dioxane, and solvent naphtha.

25 During the condensation, water issplit off.

In the preferred form of this invention, the alcohols used are aliphatic, 'monohydric'I primary alcohols containing at least eight carbon atoms;

' advantageously, 12 carbon atoms in the chain, if 30 the moreuseful phenolic detergents which are one of the objects of this invention, are to be. obtained. If the complex phenolic bases employed contain long alkyl side chains in themmatic nucleus, as for example, in the case of the 35 butyl, amyl, hexyl, octyl. lauryl, or cetyl phenols or the corresponding cresols orresorcinols, the alcohols used can be selected with chains shorter than 8 carbon atoms, so as to produce useful bactericidal soaps. It is to be understood therefore, that 40 for the purpose of producingwater-soluble com-' pounds in general, the present process can be. carcarbon atoms than eight. I

The alcohols used can be monohydric or polyried out with alcohols containing less or more 4 hydric and may belong to the aliphatic, aromatic,

hydro-aromatic, heterocyclic or alicyclic series. They may contain in addition. S-, C=0, in their molecule. For practical purposes,

,howeventhe higher aliphatic primarylalcohols v 50 such as n-octyl, lauryl, cetyl, alpha-ethyl-hexyl,

oleyl, or octadecyl alcohols are advantageously used; or polyhydric alcohols such as l,l0-deca-' methyleneglycol, and 1,12-octadecandiol. Mix tures of the above alcohols as obtained syntheti- 55' cally from the high temperatm'e-high pressure (01. zen-13o) hydrogenation of fatty glycerides or of fatty acid esters may be used, such for example,as the alcohols obtained from the reduction of the acids from cocoanut oil, palm oil, tallow, castor oil and the like, or the alcohols obtained ,from other natural fats or waxes such as spermac'eti, bees wax and wool grease. 1

Among the other alcohols which can be used there may be mentioned n -butyl alcohol, npropyl alcohol, ethylene glycol, glycerol, tril0 methylene glycol, diethylene glycol, triethylene glycol, glycol-mono-ethyl ether (known as Cellosolve"), lso-amyl alcohol, pentaerithrite, mannitol, phenoxyethanol, tetrahydro furfuryl alcohol, diethylene glycol-,mono-butyl ether (known 15 as Carbitol") and phenylethyl alcohol.

The alcohol and the'complex phenolic amine salt of the type described herein are employed for the condensation, in proportions which will allow substantially all of the primary alcohol to be chemically combined with the salt of the phenolic base. These proportions correspond substantially to one primary alcoholic hydroxyl group for one reactive-nitrogen atom in the complex phenolic amine salt. Where the complex phenolic amine salt contains two reactive nitrogen atoms, one may employ oneor two moi equivalentsof a primary monohydric alcohol, or one mol equivalent of aprimary dihydric alcohol.

As a rule any secondary or tertiary alcoholic groups which may be present in the primary alcohols used, do not condense, but split off water to form an unsaturated bond. V

The complex phenolic base which serves as the intermediate for the preparation of these new 36 soaps, is obtained by condensing any phenol (or fusible, soluble ilovolack type phenolic-formaldehyde'resin) having a replaceable nuclear hydrogen atom and which contains no free acidity or acidic groups. with at least one molecular 40 equivalent each of formaldehyde and an aliphatic or alicyclic secondary amine having the formula X-NH-Xi wherein X-and X1 are each alkyl or ring methylene groups. Such products are in appreciable decomposition in a high vacuum; others are amorphous bals'ams and cannot be distilled without decomposition. A few of them are crystalline. They are all phenols which combine with acids to form amine salts. For the purpose of this invention they are combined with hydro halides suchas hydrogen chloride or hydrogen; bromide, or with'sulfurlc acid, to form the corresponding complex phenolic amine salts; These salts are the saw materials employed in the pressome cases oils which can be distilled without 4 eat invention for the condensation with the alcohols mentioned herein.

The products obtained by the condensation of reacting proportions of the alcohol with these hydrohalide or sulfate salts, are generally of a sticky, waxy to oilyconsistency. Some of them are definitely crystalline. They are all readily soluble in water.

By the present process a great variety of phenolic water-soluble compounds can be prepared the uses of which are'in many cases dependent upon the .nature of the groups or radicals'present, which are in turn dependent upon the nature of the phenol, secondary amine, acid, and alcohol used, as shown in the examples.

Among the phenols which can be used for the purpose of obtaining the desired complex phenolic amines by the condensation with formaldehyde and the secondary amine, there may be mentioned the following:

Phenol, 0-, m-, and p-cresol, 1,3,5-xylenol, any of the propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, lauryl, or cetyl phenols or the corresponding cresols or resorcinols, 0-, m-, or p-phenylphenol, benzylphenol, cyclohexylphenol, thymol, guaiacol, resorcinal, pyrocatechol, hydroquinone, alpha or beta-naphthol, bis-(p-hydroxydiphenyl) -dimethylmethane, and their nuclear halogen, alkyl, alkoxy, or acyl derivatives.

The secondary amines used can be dimethylamine, diethyl-amine, methyl ethylamine, dibutylamine, morpholine, piperazine, piperldine and the like.

Upon reacting the secondary amine, the phenol, and the formaldehyde together for 24 hours at room temperature or for several hours on the steam bath, alone, or in an inert solvent such as alcohol, the complex phenolic amine will usually separate as a sticky mass or sirup. Sometimes the product crystallizes. The phenolic amine after removal of unchanged starting materials 'is then converted into its hydrohalide or sulfate by reaction preferably with the dry gas or acid, and

the substantially anhydrous salt thus obtained is heated with the alcohol until the product becomes soluble in water.

In view of the complex nature of the starting materials and the amorphous character of the products formed which are doubtless derivatives of polynuclear aromatic systems analogous to the Novolack type resins, it is not possible to state their exact chemical nature. It appears, however, that they are all phenols containing nitrogen together with the negative radicals of the alcohols and of the acids used. The products can in many cases, be coupled with diazotized aromatic amines to give dyestuffs.

In order to more clearly illustrate this invention, the following examples are given. In these.

' The pale yellow oil boiling at about -105 C./.7-8 mm. ,was collected. It is soluble in either dilute sodium hydroxide solution or in dilute hydrochloric acid; Condensate B.198 grams ortho-cresol, grams 35% dimethylamine solution, and 100 grams 30% formaldehyde solution were condensed as above. The product obtained was a pale yellow oil boiling at about 104 C./4 mm.

Condensate C.From l mol. each of 1,3,5-xylenol, formaldehyde and dimethylamine, treated as above, the product obtained boiled at -145 C./12 mm. and crystalized in colorless plates melting at about 40 C.

Condensate D.From 1 mol. each of paravchlorophenol, formaldehyde, and dimethylamine, treated as above, the product obtained was a pale yellow oil boiling at C./17 mm.

Condensate E.From 1 mol. each of a,a,'y,'ytetramethyl-butyl-phenol, formaldehyde, and dimethylamine, in alcoholic solution. Product formed colorless crystals melting at 69 C. 2

Condensate F.From 1 mol. each of a,a,'y,'ytetramethyl-butyl-phenol, formaldehyde, and piperidine, in alcoholic solution. Product formed colorless crystals melting at 69 C.

- Condensate G .From 1 mol. each ortho-phenyl phenol, formaldehyde and dimethylamine, in alcoholic solution. Product formed colorless crystals melting at 112-113 C. The isomer prepared from para-phenyl-phenol melts at 90 C.

Condensate H.-From 1 mol. each of betanaphthol, formaldehyde, and dimethylamine, in alcoholic solution; melting point 75 C.

Condensate I.From 1 mol. each of bis-(p-hydroxy-diphenyD-dimethyl methane, formaldehyde and diethylamine in alcoholic solution. 35

Product was a sticky viscous mass.

Condensate J.--From 1 mol. each of phenol, formaldehyde and morpholin. Product-colorless crystals, melting point 95-96 C.

Example 1.Condensate andlauryl alcohol 38 grams condensate A were dissolved in 100 grams toluene in a flask fitted with a stirrer, dropping funnel, reflux condenser and automatic water separator; and gradually converted to its 4 sulfate by adding slowly with cooling and stirring 25 grams 98% sulfuric acid so that the temperature did not exceed 40 C. The complex phenolic amine salt separated as a viscous oil. To the mixture, 46 grams technical lauryl alcohol (obtained 5 some of the toluene, and the latter automati- 5;

cally returned to the flask, while the water was separated. When no more water came off, a clear colorless solution was obtained. The toluene was then removed by distillation under reduced pressure (50 mm.) on the steam bath. Theresidual product was a viscous, sticky, somewhat reddish oil. It was readily and completely soluble in cold water as well as in alcohol, or in benzene.

A 5% aqueous solution ,of the product was acidic'and faintly opalescent and very foamy and soapy. It maintained its foamy soapy character in hard water or in acidic, neutral, or alkaline solution even on boiling, and may be used in either acid, alkaline or neutral solutions as a detergent, wetting, emulsifying or dispersing agent. In its acidicform it precipitates gelatine and may find use as a leather tanning-agent.

Condensate "A and alpha-ethyl-n-hexanol. 38 grams condensate A was converted to the complex phenolic amine sulfate with'25 grams 75 and the mixture boiled-under reflux boiled for 1% hours with 32.5 grams alpha-ethyln-hexanol, in the same manner as described above. Upon removing the toluene from the clear solution thus obtained, by evaporation under vacuum. the residual product formed a when shaken. It is an excellent wetting-out agent for dyeing textiles.

Condensate "A and LIO-decamethylene glycol.-38 grams condensate A in grams toluene was converted to the amine salt by means of 25 grams 98% sulfuric acid at 25-35" C. The mixture was boiled under reflux-with 22 grams 1,10-decamethylene glycol for 1 /2 hours as described above. Two layers were formed on cooling.

was a. somewhat brittle reddish sticky soapy. When neutralized with dilute potassium hydroxide, it gave a solution having marked wetting-out properties for cotton. I

In another experiment the above quantity of LIO-decamethylene glycol used was cut in half. The product was in general, similar in its physical properties to the preceding one, but was somewhat harder.

Condensate A and 1,12-octadecanediol.15 grams condensate Af in 100 grams toluene was converted by means of 10 grams 98% sulfuric acid at 25-35 C. into the amine sulfate. 28.5 grams 1,12-oetadecanediol (from the catalytic hydrogenation of castor oil) was added and the mixture was boiled with stirring under reflux until 2 cc. water had comeover in'the automatic'water separator. The clear solution obtained was evaporated to dryness on steam bath at 12 mm. The residual product was a viscous, colorless waxy mass. Its aqueous solution forms a gooddetergent. r

Condensate A and oleyl aZcohol.-The proportions used were: Y

15 grams condensate A" in '75 grams toluene 10 grains 98% sulfuric acid 26.8 grams oleyl' alcohol m The. amine salt was first prepared at 20-30 C. The oleyl alcohol was then added and. mixture was boiled 1 hours as described above. The solvent was then removed in vacuo on steam bath.

The product was a pale reddish-viscous oily mass. Its aqueous solution was very foamy and soapy. when neutralized with triethanolamine it gave a soap having good detergent properties.

Condensate 24 and cetyl alcohol.Th e proportions used were: V

15 grams condensate "A." in '75 grams toluene 10 grams 98% sulfuric acid 25 grams cetyl alcohol The condensation and working up of the product were similar to that above. The product was a viscous waxy mass: It may be used as a soap.

Condensate A and e e y-tatramethyl-butylphenocy-ethanol.-The proportions used were:

38 grams condensate A in 100 grains toluene neutralized with 25 grams 98% sulfuric acid at 25-35 C. 62.5 grams a,a,'y,'y-tetramethyl-butylphenoxy-ethanol using roto- 2.045.517 "98% sulfuric acid m 100 grams toluene, and

i mass. Its aqueous solution was very foamy andmatic water separator until a clear solution was obtained. The time required was lA-Zhours. The toluene was then distilled off in vacuo on steam bath. Product was a. viscous solid. Its aqueous solutions foam strongly when shaken. Itmay be usedasasoap:

Erample 2. Condensate "B", and lauryl alcoho solution was foamy and precipitated gelatine.

Upon neutralization of the aqueous solution with dilute caustic soda a clear solution possessing high wetting and detergent properties was obtained.

Condensate "B and cetyl alcohol-The proportions used were: I i

41 gramscondensate B (made from metapara-cresol mixture: b. p. -125" C./l0 mm.)

100 grams toluene 25 grams 96% sulfuric acid 25 grams eetyl alcohol The reagents were mixed in the order shown as described above. The mixture was boiled with stirring for two hours so that the water formed was separated and the toluene which distilled oil was continuously replaced. Upon removal of the toluene in vacuo, the residual product was a viscous somewhat waxy mass the aqueous solution ammonia it gave a good detergent. Enample 3.-Condensate 0" and lauryl alcohol the order shown at of which is soapy. Upon. neutralization with.

2540? 'C. The mixture was boiled 1 -2 hours as described in Example 1. solvent, the residual product was a pale reddish sticky balsam. Its aqueous solution foams strongly when shaken and can be used as an acidic detergent, or'the solution can be men-- tralized with sodium carbonate for use on cotton.

Example rfiondensate D and lauryl alcohol Example 5.-0ondensate a and Zduryl alcohol The hydrochloride 0! condensate E was pre- After removal of the pared by passing dry hydrogen chloride into an ether solution of the base.

7 and dried. The. hydrochloride was a colorless crystalline substance A mixture of 15 grams of this hydrochloride and 9 grams oi. lauryl alcohol was heated under reflux in an oil bath at -165" C. for iy -z It was filtered off 70 hours. Acle ar colorless oil formed, which gradually solidified to a waxy, crystalline mass. It was readily soluble in water to give a foamy,

soapy solution having very high bactericidal powgrams of the hydrochloride of condensate E and 5 grams of glycerol wa heated under reflux at 160-170 C. for two hours. The product obtained dissolved in water to give a foamy, soapy solution.

Condensate E and diethylene glycol.To a solution of 26.3 grams condensate E in 100 cc. toluene there was added 11 grams 98% sulfuric acid, while stirring and cooling to 20-251 C. The complex phenolic amine sulfate separates as a sticky mass. To the mixture there was added 10.6 grams diethylene glycol. The mixture was then boiled under reflux for 1 hours so that the water which formed distilled oil while the toluene was continuously returned to the regrams condensate E" there was added at 5-10 per being toluene.

and dried in vacuo at 90-100 C. It formed a action vessel. Two layers were formed, the up- The lower layer was run off viscous reddish mass which dissolved readily in water to a soapy solution.

Condensate"E.and ethyl a1cohol.-To 26.3

C. with stirring 10 grams 98% sul uric acid and then 10 grams absolute alcohol. The mixture was heated on steam bath at 90 100 C. for 3 hours. The clear reddish soiuuoii obtained was evaporated to dryness in vacuo on steam bath..

The residue was a reddish brittle amorphous mass. A 5%solution thereof in water is clear and can be used as a wetting-out agent. By neutralization with triethanolamine, a water-soluble salt is obtained having high bactericidal power. Example 6.-Condensate "F and-lauryl alcohol butanol, glycerol, or alpha-ethyl-n-hexanol to" yield similar condensation products.

'densation products.-

Example 7.Condensate G and lauryl alcohol .22.! grams condensate G -(mlting point 112 113 C.) in 100 cc. toluene was treated with 10.5

grams 98% sulfuric acid at 20-25" C. Lauryl,al-. cohol (18.6 grams) was then added and the mixture boiled for'l hours under reflux so that water which formed was automatically separated.

Upon evaporation ofthe solvent in vacuo, a viscous mass was obtained. Its aqueous solution foams strongly when shaken, and is a powerful antiseptic. I

In placeof the condensate G, melting point 112-113 C. the isomeric product, melting point C. made from para-phenylphenol was used in the same manner. The product was an amorphous mass, readily soluble in water.

The lauryl alcohol can be replaced by molecularly equivalent amounts of cetyl. oleyl, octadecyl or n-oc'tyl alcohol to give analogous con- Condensate E and glyceroL-A mixture of 15 Example 8.Condensate "H" and lauryl alcohol Example 9.Condensate ,I and lauryl alcohol The proportions used were:

28.5 grams condensate 1" in cc. dioxane 11 grams 98%sulfuric acid 18.6 grams lauryl alcohol. The sulfate of the base was boiled 2% hours under reflux with the toluene solution of the lauryl alcohol. Upon removal of the solvent in vacuo a reddish mass was obtained which in aqueous solution gives soap-like foamy solutions 4 capable of precipitating gelatine.

The lauryl alcohol can be replaced by 0.1 mol. respectivelyof n butanol, alpha-ethyl hexanol, or glycerol to yield water-soluble, glue precipitating condensation products.

Example 10.Condensate J and lauryl alcohol To a solution of 19.3 grams condensate J" in "75 cc. toluene, 10.3 grams 98% sulfuric acid-was added with cooling at 2030 C. Then 18.6 grams lauryl alcohol was added. The mixture was boiled for 1 hours under reflux with stirring so that the water formed was continuously removed while the toluene was returned to the flask. The clear solution was evaporated to dryness in vacuo. The residue was a pale soap-like mass. Its aqueous solution is a good wetting-out agent. When neutralized with caustic soda, the solution is a. good detergent.

In the above examples, certain deviations may be made without departing from the spirit of the invention such for example as using a mixtureof alcohols, or a mixture of phenols or a mixture of the secondary amines. The temperatures may be adjusted to meet the particular requirements which'mav vary somewhat with the nature of the salt or of the alcohol used. The phenols used do notmecessarily have to be pure; the crude products known as tar acids or cresylic acids maybe used for producing cheap germicidal compounds of the type described. The term phenol as employed broadly herein refers to both monoamines used are those set forth specifically here- 70,

in, nevertheless'the reaction is applicable to all phenols and aliphatic or alicyclic secondary amineswhich are free from acidic groups.

The water-soluble products obtained by the x 7 present process contain phenolic hydroxyl news 75 and possess the typical properties of phenols. They all precipitate gelatine more or less when in the acidified form. They may be used in washing, bucking, tanning, mordanting and dyeing operations; in hydrolyzing fats to fatty acids and glycerine; for emulsifying oils or fats in water; for breaking petroleum emulsions; for dispersing pigments and dyestuifs; for additions to soaps obtained by the intercondensation of a phenol with at least molecularly equivalent quantities each of formaldehyde and avsecondary amine oi the formula X-NH-X1 wherein X and X1 are each alkyl or ring methylene groups; said heating being carried out at a temperature capable of eifecting the splitting off of water from the reaction mixture.

2. A process for preparing phenolic water-sol v uble compounds, which comprises heating reacting proportions of a primary monohydric alcohol with a member of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the intercondensation of a phenol with at least molecularly equivalent quantities each of formaldehyde and a secondary amine of the formula X-NH-Xi wherein X and K1 are each alkyl or ring methylene groups; said heating being carried out at a temperature capable of effecting the splitting off of water from the reaction mixture.

3. A process for preparing phenolic water-soluble compounds, which comprises heating reacting proportions of a primary polyhydric alcohol with a member of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the intercondensation of a phenol with at least molecularly equivalent quantities each of formaldehyde and a secondary amine of the formula X-NH-Xi wherein a X and X1 are each alkyl or ring methylene-groups;

said heating being carried out at a temperature capable of effecting the splitting oil of water from the reaction mixture. a

4. A process for preparing phenolic water-soluble compounds which comprises, heating reacting proportions of a primary fatty alcohol having more than seven carbon atoms with a member of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the i-ntercondensation of a phenol with at least molecularly equivalent quantities each of formaldehyde and a secondary amine of the formula XNH-X1 wherein X and K1 are each alkyl or ring methylene groups; said heating being carried out-at a temperature capable of effecting the splitting ofi of water from the reaction mixture.

"'5. A process for preparing phenolic water-soluble compounds; which comprises heating reacting proportions of a primary fattyalcohol. having more than seven carbon atoms with the sulfuric acid salt of a complex phenolic amine obtained by the 'intercondensation of substantially one molecular equivalent each of a phenol, formaliiehyde and dimethylamine; said heating being carried out at a temperature capable of ef ecting the splitting oil of water from the reaction mix- 6. A process for preparing phenolic water-soluble compounds, which comprises heating substantially one molecular equivalent of a primary 5 aliphatic monohydric alcohol having more than seven carbon atoms with the sulfuric acidsalt of a complex phenolic amine obtained by the inter-- condensation of substantially one molecular equivalent' each of a phenol, formaldehyde and dimethylamine; said heating being carried out at a temperature capable of eifecting the splitting-off of water from the reaction mixture.

'7. A process for preparing phenolic water-soluble compounds, which comprises heating substantially' one molecular equivalent of a primary aliphatic monohydric alcohol having more than seven carbon atoms with the sulfuric acid salt of a complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of phenol, formaldehyde and dimethylamine;' said heating being carried out at a temperature capable of effecting the splitting oil of water from the reaction mixture.

8. A process for preparing phenolic water-soluble compounds which comprises heating substantially one molecular equivalent of laury'l alcohol with the sulfuric acid salt of a complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of a phenol, formaldehyde and dimethylamine; said heating being carried out at a temperature capable of effecting the splitting off ofwater from the reaction mixture.

9. A process for preparing phenolic water-soluble compounds which comprises heating substantially one molecular equivalent of lauryl alcohol with the sulfuric acid salt of a complex'phenolic amine obtained by the intercondensatlon of substantially one molecular equivalent each of phenol, formaldehyde and dimethylamine; said heating being carried out at a temperature capable of effecting the splitting off of water from the reaction mixture.

10. A process for preparing phenolic water-soluble compounds which comprises heating substantially one molecular equivalent of lauryl alcohol with the sulfuric acid salt of a complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of cresol, formaldehyde and dimethylamine; said heating being carried out at a temperature capable of effecting the splitting ofl of water from the reaction mixture. v

ILA water-soluble condensation product of (1) an alcohol containing a primary alcohol group, and (2) a member of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the intercondensation ofa phenol with at least molecular equivalent quantities each of formaldehyde and a secondary amine of the formula X-NH-X1 wherein X and K1 are each alkyl or ring methylene groups.

12. A water-soluble condensation product of (l) a primary monohydricalcohol and (2) a member of the group consisting of the hydrohalideand sulfuric acid salts of complex phenolic amines obtained by the intercondensation of a phenol with at least molecular equivalent quantities each of formaldehyde and a secondary amine of the formula XNHX1 wherein X and X1 are each alkyl or ring methylene groups.

13. A water-soluble condensation product of (1) a primary polyhydric alcohol (2) a mem- 7 her of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the intercondensation of a phenol with at least molecular equivalent quantities each of formaldehyde and a secondary amine of the formula X-NH'X1 wherein X and K1 are each alkyl or ring methylene groups.

14. A water-soluble condensation product of (1) a primary fatty alcohol having more than seven carbon atoms and (2) a member of the group consisting of the hydrohalide and sulfuric acid salts of complex phenolic amines obtained by the intercondensation of a' phenol with at least molecular equivalent quantities each of formaldehyde and a secondary amine of the formula X-NHX1 wehein X and K1 are each alkyl ori ring methylene groups.

15. A water-soluble condensation product of (1) a primary fatty alcohol having more than seven carbon atoms and (2) the sulfuric acid salt'of a complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of a phenol, formaldehyde and dimethylamine.

16. A water-soluble condensation product of one molecular equivalent each of phenol, formaldehyde, and dimethylamine.

1'7. A water-soluble condensation product of (l) lauryl alcohol and (2) a sulfuric acid salt of the complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of a phenol, formaldehyde, and dimethylamine.

18. A water-soluble condensation product of (1) lauryl alcohol and (2) a sulfuric acid salt of the complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of phenol, formaldehyde, and dimethylamine.

19. A water-soluble condensation product of 1) lauryl alcohol and (2) a sulfuric acid salt of the complex phenolic amine obtained by the intercondensation of substantially one molecular equivalent each of cresol, formaldehyde, and dimethylamine.

20. A water-soluble condensation product of (1) lauryl alcohol and (2) a sulfuric acid salt of the complex phenolic amine obtained by the. in-

tercondensation of substantially one molecular equivalent each of phenylphenol, formaldehyde, 

